Multi-functional cyclic siloxane compound, a siloxane-based polymer prepared from the compound and a process for preparing a dielectric film by using the polymer

Abstract

A multi-functional cyclic siloxane compound (A), a siloxane-based (co)polymer prepared from the compound (A), or compound (A) and at least one of a Si monomer having organic bridges (B), an acyclic alkoxy silane monomer (C), and a linear siloxane monomer (D); and a process for preparing a dielectric film using the polymer. The siloxane compound of the present invention is highly reactive, so the polymer prepared from the compound is excellent in mechanical properties, thermal stability and crack resistance, and has a low dielectric constant resulting from compatibility with conventional pore-generating materials. Furthermore, a low content of carbon and high content of SiO 2 enhance its applicability to the process of producing a semiconductor, wherein it finds great use as a dielectric film.

1. A siloxane-based polymer having repeat units of a cyclic Si—O structure, prepared by hydrolyzing and polycondensing at least one multi-functional cyclic siloxane compound of formula (1) alone, or in combination with at least one monomer selected from the group consisting of the compounds of formulas (2)-(5), in an organic solvent in the presence of an acid or alkali catalyst and water: 
       
         
           
           
               
               
           
         
         wherein, 
         R 1  is a hydrogen atom, a C 1-3  alkyl group or a C 6-15  aryl group; 
         R 2  is SiX 1 X 2 X 3  (wherein, each of X 1 , X 2  and X 3  is, independently, a hydrogen atom, a C 1-10  alkyl group, a C 1-10  alkoxy group or a halogen atom, provided that at least one of them is hydrolysable); and 
         p is an integer from 3 to 8, 
       
       
         
           
           
               
               
           
         
         wherein, 
         R 1  is a hydrogen atom, a C 1-3  alkyl group or a C 6-15  aryl group; 
         each of X 1 , X 2  and X 3  is, independently, a hydrogen atom, a C 1-3  alkyl group, a C 1-10  alkoxy group or a halogen atom, provided that at least one of them is hydrolysable; 
         m is an integer from 0 to 10; and 
         p is an integer from 3 to 8,
   X 3 X 2 X 1 Si-M-SiX 1 X 2 X 3   (3) 
 
         wherein, 
         each of X 1 , X 2  and X 3  is, independently, a hydrogen atom, a C 1-3  alkyl group, a C 1-10  alkoxy group or a halogen atom, provided that at least one of them is hydrolysable; and 
         M is a single bond, a C 1-10  alkylene group, or a C 6-15  arylene group,
   (R 1 ) a Si(OR 2 ) 4-n   (4) 
 
         wherein, 
         R 1  is a hydrogen atom, a C 1-3  alkyl group, a C 6-15  aryl group or a halogen atom, 
         R 2  is a hydrogen atom, a C 1-3  alkyl group or a C 6-15  aryl group, provided that at least one of them is hydrolysable; and 
         n is an integer from 0 to 3, and 
       
       
         
           
           
               
               
           
         
         wherein, 
         each of R 1  is a hydrogen atom, a C 1-3  alkyl group, a C 1-10  alkoxy group, a hydroxy group or a halogen atom, provided that at least one of them is hydrolysable; and 
         n is an integer from 0 to 30. 
       
     
     
       2. The siloxane-based polymer according to  claim 1 , wherein the cyclic siloxane compound represented by formula (1) is selected from the group consisting of the compounds of formulas [6] and [9]-[10]: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       3. The siloxane-based polymer according to  claim 1 , wherein the monomer represented by formula (2) or (3) is specified as a compound of formula (13), (14) or (15): 
       
         
           
           
               
               
           
         
       
     
     
       4. The siloxane-based polymer according to  claim 1 , wherein the compound represented by formula (4) is specified as a compound of formula (12), (16) or (17): 
       
         
           
           
               
               
           
         
       
     
     
       5. The siloxane-based polymer according to  claim 1 , wherein the compound represented by formula (5) is specified as a compound of formulas (19)-(22): 
       
         
           
           
               
               
           
         
         wherein, 
         n is an integer from 0 to 30. 
       
     
     
       6. The siloxane-based polymer according to  claim 1 , wherein the acid catalyst is hydrochloric acid, nitric acid, benzene sulfonic acid, oxalic acid, formic acid or a mixture thereof, and the alkali catalyst is potassium hydroxide, sodium hydroxide, triethylamine, sodium bicarbonate, pyridine or a mixture thereof. 
     
     
       7. The siloxane-based polymer according to  claim 1 , wherein molar ratio of total monomers to be polymerized and the acid or base catalyst ranges from 1:1×10 −5 to 1:10. 
     
     
       8. The siloxane-based polymer according to  claim 1 , wherein molar ratio of total monomers to be polymerized and the water ranges from 1:1 to 1:100. 
     
     
       9. The siloxane-based polymer according to  claim 1 , wherein the hydrolysis and the polycondensation or copolymerization are performed at 0-200° C. for 0.1-100 hrs. 
     
     
       10. The siloxane-based polymer according to  claim 1 , wherein the organic solvent is an aliphatic hydrocarbon solvent such as hexane or heptane; an aromatic hydrocarbon solvent such as anisol, mesitylene or xylene; a ketone-based solvent such as methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, cyclohexanone or acetone; an ether-based solvent such as tetrahydrofuran or isopropyl ether; an acetate-based solvent such as ethyl acetate, butyl acetate or propylene glycol methyl ether acetate; an alcohol-based solvent such as isopropyl alcohol or butyl alcohol; an amide-based solvent such as dimethylacetamide or dimethylformamide; a silicon-based solvent; or a mixture thereof. 
     
     
       11. The siloxane-based polymer according to  claim 1 , wherein the polymer has a Mw of 3,000-300,000.